Cyclic phosphorus containing flame retardant compounds

Abstract

Certain (1,3,2-dioxaphosphorinanemethan) amine compounds, which are useful as flame retardant compounds, are disclosed. The compounds are particularly useful in polyurethane compositions.

We claim: 
     
       1. A compound having the formula: A 3-Y  --N--B Y   wherein A is ##STR10## R 1  and R 2  are independently selected from the group consisting of hydrogen, halogens, alkyl groups having from 1 to 4 carbon atoms, halogenated alkyl groups having from 1 to 4 carbon atoms, aryl and halogenated aryl groups having from 6 to 8 carbon atoms, Y is 1 or 2 and each B is independently selected from the group consisting of hydrogen, alkyl groups having from 2 to about 8 carbon atoms, halogenated alkyl groups having from 2 to about 8 carbon atoms, aryl and halogenated aryl groups having from 6 to about 8 carbon atoms and wherein the compound is a solid at ambient temperature, and with the proviso that when Y is 2 and B is ethyl that R 1  and R 2  cannot both be methyl.     
     
     
       2. The compound of claim 1 wherein R 1  and R 2  are each independently selected from the group consisting of hydrogen, halogens, alkyl groups having from 1 to 4 carbon atoms and halogenated alkyl groups having from 1 to 4 carbon atoms. 
     
     
       3. The compound of claim 2 wherein R 1  and R 2  are chloromethyl. 
     
     
       4. The compound of claim 1 wherein R 1  and R 2  are each independently selected from the group consisting of hydrogen, halogens, aryl and halogenated aryl groups having from 6 to 8 carbon atoms. 
     
     
       5. A composition of matter comprising an organic polymeric material and a fire retardant amount of a compound having the formula: A 3-Y  --N--B Y   wherein A is ##STR11## R 1  and R 2  are independently selected from the group consisting of hydrogen, halogens, alkyl groups having from 1 to 4 carbon atoms, halogenated alkyl groups having from 1 to 4 carbon atoms, aryl and halogenated aryl groups having from 6 to 8 carbon atoms, Y is 1 or 2 and each B is independently selected from the group consisting of hydrogen, alkyl groups having from 2 to about 8 carbon atoms, halogenated alkyl groups having from 2 to about 8 carbon atoms, aryl and halogenated aryl groups having from 6 to about 8 carbon atoms and wherein the compound is a solid at ambient temperature, and with the proviso that when Y is 2 and B is ethyl that R 1  and R 2  cannot both be methyl.     
     
     
       6. The composition of matter of claim 5 wherein the organic polymeric material is selected from the group consisting of polyurethane foams, other polyurethane containing compositions, and compositions containing polyesters, styrenic polymers, polyvinyl chloride, polyvinyl acetates or polycarbonates. 
     
     
       7. The composition of matter of claim 6 wherein the organic polymeric material is a polyurethane foam. 
     
     
       8. The composition of matter of claim 5 wherein R 1  and R 2  are each independently selected from the group consisting of hydrogen, halogens, aryl and halogenated aryl groups having from 1 to 4 carbon atoms. 
     
     
       9. The composition of matter of claim 8 wherein R 1  and R 2  are halogenated methyl groups. 
     
     
       10. The composition of matter of claim 5 wherein R 1  and R 2  are each independently selected from the group consisting of hydrogen, halogens, aryl and halogenated aryl groups having from 6 to 8 carbon atoms. 
     
     
       11. The composition of matter of claim 5 wherein Y is 1 and each B is independently selected from the group consisting of hydrogen, alkyl groups having from 2 to about 8 carbon atoms and halogenated alkyl groups having from 2 to about 8 carbon atoms. 
     
     
       12. The composition of matter of claim 5 comprising a polyurethane foam and a fire retardant amount of a compound having the formula: A 3-Y  --N--B Y   wherein A is ##STR12## Y is 1 or 2 and each B is independently selected from the group consisting of hydrogen, alkyl groups having 2 to about 8 carbon atoms, halogenated alkyl groups having from 2 to about 8 carbon atoms, aryl and halogenated aryl groups having from 6 to about 8 carbon atoms and wherein the compound is a solid at ambient temperature, and with the proviso that when Y is 2 and B is ethyl that R 1  and R 2  cannot both be methyl.     
     
     
       13. A process for the production of compounds having the formula: A 3-Y  --N--B Y   wherein A is ##STR13## R 1  and R 2  are independently selected from the group consisting of hydrogen, halogens, alkyl groups having from 1 to 4 carbon atoms, halogenated alkyl groups having from 1 to 4 carbon atoms, aryl and substituted aryl groups having from 6 to 8 carbon atoms and halogenated aryl and halogenated substituted aryl groups having from 6 to 8 carbon atoms, Y is 1 or 2 and each B is independently selected from the group consisting of hydrogen, alkyl groups having from 2 to about 8 carbon atoms, halogenated alkyl groups having from 2 to about 8 carbon atoms, aryl and substituted aryl groups having from 6 to about 8 carbon atoms and halogenated aryl and halogenated substituted aryl groups having from 6 to about 8 carbon atoms, comprising the steps of:     (a) adding phosphorus trichloride to a mixture of a 1,3-diol derivative and water and an organic solvent at a temperature of from about 10° C. to about 60° C. to produce a 5,5-di-substituted 1,3,2-dioxaphosphorinane-2-oxide having the general formula: ##STR14## wherein R 1  and R 2  are independently selected from the group consisting of hydrogen, halogens, alkyl groups having from 1 to 4 carbon atoms, halogenated alkyl groups having from 1 to 4 carbon atoms, aryl and substituted aryl groups having from 6 to 8 carbon atoms and halogenated aryl and halogenated substituted aryl groups having from 6 to 8 carbon atoms;   (b) purifying the 5,5-di-substituted 1,3,2-dioxaphosphorinane-2-oxide;   (c) reacting the 5,5-di-substituted 1,3,2-dioxaphosphorinane-2-oxide, paraformaldehyde and an amine having the general formula:   B Y  NH 3-Y , wherein Y is 1 or 2 and each B is independently selected from the group consisting of hydrogen, alkyl groups having from 2 to about 8 carbon atoms, halogenated alkyl groups having from 2 to about 8 carbon atoms, aryl and substituted aryl groups having from 6 to about 8 carbon atoms and halogenated aryl and halogenated substituted aryl groups having from 6 to about 8 carbon atoms in an organic solvent to produce a (1,3,2-dioxaphosphorinanemethan) amine compound having the general formula:     A 3-Y  --N--B Y   wherein A is ##STR15## R 1  and R 2  are independently selected from the group consisting of hydrogen, halogens, alkyl groups having from 1 to 4 carbon atoms, halogenated alkyl groups having from 1 to 4 carbon atoms, aryl and substituted aryl groups having from 6 to 8 carbon atoms and halogenated aryl and halogenated substituted aryl groups having from 6 to 8 carbon atoms, Y is 1 or 2 and each B is independently selected from the group consisting of hydrogen, alkyl groups having from 2 to about 8 carbon atoms, halogenated alkyl groups having from 2 to about 8 carbon atoms, aryl and substituted aryl groups having from 6 to about 8 carbon atoms and halogenated aryl and halogenated substituted aryl groups having from 6 to about 8 carbon atoms; and     (f) purifying and drying the (1,3,2-dioxaphosphorinanemethan) amine compound.   
     
     
       14. A process for the production of compounds having the formula: A 3-Y  --N--B Y   wherein A is ##STR16## Y is 1 or 2 and each B is independently selected from the group consisting of hydrogen, alkyl groups having from 2 to about 8 carbon atoms, halogenated alkyl groups having from 2 to about 8 carbon atoms, aryl and substituted aryl groups having from 6 to about 8 carbon atoms and halogenated aryl and halogenated substituted aryl groups having from 6 to about 8 carbon atoms comprising the steps of:     (a) adding phosphorus trichloride to a mixture of neopentyl glycol and water and an organic solvent at a temperature of from about 10° C. to about 60° C. to produce a 5,5-dimethyl 1,3,2-dioxaphosphorinane-2-oxide having the general formula: ##STR17## (b) purifying the 5,5-dimethyl 1,3,2-dioxaphosphorinane-2-oxide; (c) reacting the 5,5-dimethyl 1,3,2-dioxaphosphorinane-2-oxide, paraformaldehyde and an amine having the general formula   B Y  NH 3-Y , wherein Y is 1 or 2 and each B is independently selected from the group consisting of hydrogen, alkyl groups having from 2 to about 8 carbon atoms, halogenated alkyl groups having from 2 to about 8 carbon atoms, aryl and substituted aryl groups having from 6 to about 8 carbon atoms and halogenated aryl and halogenated substituted aryl groups having from 6 to about 8 carbon atoms, in an organic solvent with an acid catalyst to produce a (1,3,2-dioxaphosphorinanemethan) amine compound having the general formula:     A 3-Y  --N--B Y   wherein A is ##STR18## Y is 1 or 2 and each B is independently selected from the group consisting of hydrogen, alkyl groups having from 2 to about 8 carbon atoms, halogenated alkyl groups having from 2 to about 8 carbon atoms, aryl and substituted aryl groups having from 6 to about 8 carbon atoms and halogenated aryl and substituted aryl groups having from 6 to about 8 carbon atoms; and     (d) purifying and drying the (1,3,2-dioxaphosphorinanemethan) amine compound.   
     
     
       15. The composition of claim 1 wherein Y is 1. 
     
     
       16. The composition of claim 5 wherein Y is 1.